Process for the Preparation of Ethylene Polymers Using a Number of Reactors Arranged in Series

ABSTRACT

The present invention relates to a process for the preparation of ethylene polymers using a number of reactors arranged in series comprising the steps in which 
     a) ethylene, a diluent, a catalyst, a co-catalyst and optionally comonomers and hydrogen are introduced into a first reactor,
 
b) polymerization of ethylene and optionally comonomers is carried out in the reaction mixture of said first reactor to make ethylene polymers,
 
c) reaction mixture is discharged from said first reactor,
 
d) said reaction mixture and fresh ethylene and optionally comonomers and hydrogen are introduced into the consecutive reactor to make additional ethylene polymers,
 
e) said reaction mixture is discharged from said consecutive reactor and introduced into the further consecutive reactor, if any, with fresh ethylene and optionally comonomers and hydrogen to make additional ethylene polymers, steps c) and d) are repeated until the last reactor of the series,
 
f) reaction mixture is discharged from last reactor of the series and ethylene polymers are recovered,
 
wherein,
 
additional co-catalyst is injected in at least a subsequent reactor of the series.
 
     Advantage of the process of the present invention is mainly to decrease catalyst consumption for the same polyethylene production, in other words to increase the productivity. In a most preferred embodiment the process of the present invention is carried out in two loop reactors under slurry conditions.

FIELD OF THE INVENTION

The present invention is a process for the preparation of ethylenepolymers using a number of reactors arranged in series. It relates, inparticular, to a process wherein a catalyst and a co-catalyst areinjected in a first reactor and additional co-catalyst is injected in atleast a subsequent reactor. By way of example, the process according tothe present invention may be applied in a double loop polymerizationreactor consisting of two liquid full loop reactors, comprising a firstand a second reactor connected in series by one or more settling legs ofthe first reactor connected for discharge of slurry from the firstreactor to said second reactor. In series connected reactors areparticularly suitable for the preparation of bimodal polyethylene (PE).

The Prior Art and the Technical Problem

Polyethylene (PE) is synthesized via polymerizing ethylene (CH₂═CH₂)monomers. Because PE is cheap, safe, stable to most environments andeasy to be processed polyethylene polymers are useful in manyapplications. According to the properties polyethylene can be classifiedinto several types, such as but not limited to LDPE (Low DensityPolyethylene), LLDPE (Linear Low Density Polyethylene), and HDPE (HighDensity Polyethylene). Each type of polyethylene has differentproperties and characteristics.

Polyethylene polymerizations are frequently carried out using monomer,diluent and catalyst and optionally co-monomers and hydrogen in reactorsarranged in series. These reactors are usually loop reactors. Thepolymerization is usually performed under slurry conditions, wherein theproduct usually consists of solid particles and is in suspension in adiluent. The slurry contents of the first reactor are circulatedcontinuously with a pump to maintain efficient suspension of the polymersolid particles in the liquid diluent. The slurry from the first reactoris discharged to the subsequent reactor connected in series by one ormore settling legs of the first reactor connected for discharge ofslurry from the first reactor to said subsequent reactor. The product isdischarged by means of settling legs, which operate on a batch principleto recover the product. Settling in the legs is used to increase thesolids concentration of the slurry finally recovered as product slurry.The product is further discharged to a flash tank, through flash lines,where most of the diluent and unreacted monomers are flashed off andrecycled. The polymer particles are dried, additives can be added andfinally the polymer is extruded and pelletized.

Prior art has already described preparation of ethylene polymers using anumber of reactors arranged in series.

U.S. Pat. No. 6,878,784 relates to a process to make a bimodalpolyethylene in a combination of a slurry polymerization and a gas-phasepolymerization.

EP 1041090 relates to a process for producing high density polyethylenein the presence of a metallocene catalyst system in two liquid full loopreactors in series, wherein in a first reactor a first polyethyleneproduct is polymerized substantially by homopolymerization of ethyleneand hydrogen, optionally with a minor degree of copolymerization ofethylene with an alpha-olefinic comonomer comprising from 3 to 8 carbonatoms, and in a second reactor serially connected to the first reactordownstream thereof a second polyethylene product is copolymerized fromethylene and an alpha-olefinic comonomer comprising from 3 to 8 carbonatoms, and a hydrogenation catalyst is introduced into the reactantsdownstream of the first reactor.

U.S. Pat. No. 6,946,521 relates to polyethylene resins, especially tothose suitable for use as pipe resins, and to a process for producingsuch resins. In a preferred arrangement, the product of a first cascadereaction zone, including the olefin monomer, is contacted with thesecond co-reactant and the catalyst system in a second cascade reactionzone to produce and mix the second polyolefin with the first polyolefinin the second reaction zone. The first and second reaction zones areconveniently interconnected reactors such as interconnected loopreactors or interconnected loop and continuously stirred reactors. It isalso possible to introduce into the second reaction zone fresh olefinmonomer as well as the product of the first reaction zone. Because thesecond polyolefin is produced in the presence of the first polyolefin amultimodal or at least bimodal molecular weight distribution isobtained. In one embodiment of the invention, the first co-reactant ishydrogen and the second co-reactant is the comonomer. Typical comonomersinclude hexene, butene, octene or methylpentene, preferably hexene. Inan alternative embodiment, the first co-reactant is the comonomer,preferably hexene.

It has now been discovered that in a process for the preparation ofethylene polymers under slurry conditions using a number of reactorsarranged in series wherein a catalyst and a co-catalyst are injected ina first reactor and additional co-catalyst is injected in at least asubsequent reactor, the off gas of the subsequent reactor is decreasedby comparison with the same process in which there is no additionalco-catalyst injected in at least a subsequent reactor. “off gas” meansthe reactor's purge of unpolymerized ethylene, unpolymerized co-monomerif any, hydrogen and insoluble gas. This off gas reduction means abetter catalyst activity in the second reactor. Capacity of the reactoris unchanged but catalyst consumption is reduced. In other words theproductivity is increased.

U.S. Pat. No. 6,407,185 relates to a process for the preparation of acomposition containing ethylene polymers comprising a polymer of meltindex MI₂ of 5 to 1000 g/10 min and a polymer of melt index MI₅ of 0.01to 2 g/10 min, the ratio of these indices being from 500 to 50,000 andthe weight ratio of the two polymers being equal to (30 to 70):(70 to30), according to which part of the ethylene, a catalyst derived from atransition metal having an intrinsic molecular weight distributiondefined by an intrinsic Mw/Mn ratio less than or equal to 10 and adeactivation constant less than or equal to 0.5 h⁻¹, and a cocatalystare introduced into a first reactor, polymerization of the ethylene iscarried out therein, a mixture comprising one of the polymers, thecatalyst and the cocatalyst is drawn off from this reactor and themixture and another part of the ethylene are introduced into a secondreactor, where ethylene is polymerized to form the other polymer. At col3 line 60-col 4 line 8 is written: “In the process according to theinvention, a plant is used comprising at least two polymerizationreactors arranged in series and connected to each other. Each reactor issupplied with ethylene. The catalyst and the cocatalyst are introducedsolely into the first reactor, in which ethylene is polymerized until apolymer is obtained which has the characteristics specific to thepolymerization conditions of this reactor. A mixture arising from thefirst reactor and comprising the polymer obtained in the latter, thecatalyst and the cocatalyst is introduced, preferably continuously, intothe second reactor. Ethylene, which is introduced into this secondreactor, is polymerized therein using the catalyst and cocatalystarising from the first reactor and polymerization conditions(temperature, concentration of transfer agent, concentration of optionalcomonomer) are used in this second reactor which are different fromthose used in the first reactor. At col 5 lines 29-33 is written: “Inthe process according to the invention, it is optionally possible tosupply the second reactor and/or, if appropriate, at least one of thefollowing reactors with fresh catalyst and/or cocatalyst. However, it ispreferable to introduce the catalyst and the cocatalyst exclusively intothe first reactor”. In the course of the opposition to the europeancounterpart EP 603935 B1 of said U.S. Pat. No. 6,407,185 the patenteeexplained the advantage to introduce the catalyst and the cocatalystexclusively into the first reactor thanks to the catalyst lowdeactivation constant. It is clear that the injection of co-catalyst inthe second reactor is not deemed to give an advantage.

U.S. Pat. No. 4,859,749 relates to a two-stage polymerization processusing a modified supported catalyst gives ethylene polymers with verygood processability and excellent finished component properties. Thesupported catalyst used is formed by reaction of a magnesium alcoholatewith a titanium-IV compound in suspension and subsequent reaction with ahalogen-containing organoaluminum compound and activation of the solidthus obtained by an aluminum trialkyl or aluminum isoprenyl (theco-catalyst). It is explained that the catalyst is introducedcontinuously and exclusively into the first reaction stage, theco-catalyst is also introduced continuously into the first stage, and ifappropriate additionally into the second stage. This introduction in thesecond stage is quoted as “appropriate” which means nothing but clearlythere is no suggestion to make said introduction to get a higherproductivity.

BRIEF DESCRIPTION OF THE INVENTION

The present invention relates to a process for the preparation ofethylene polymers using a number of reactors arranged in seriescomprising the steps in which

a) ethylene, a diluent, a catalyst, a co-catalyst and optionallycomonomers and hydrogen are introduced into a first reactor,b) polymerization of ethylene and optionally comonomers is carried outin the reaction mixture of said first reactor to make ethylene polymers,c) reaction mixture is discharged from said first reactor,d) said reaction mixture and fresh ethylene and optionally comonomersand hydrogen are introduced into the consecutive reactor to makeadditional ethylene polymers,e) said reaction mixture is discharged from said consecutive reactor andintroduced into the further consecutive reactor, if any, with freshethylene and optionally comonomers and hydrogen to make additionalethylene polymers, steps c) and d) are repeated until the last reactorof the series,f) reaction mixture is discharged from last reactor of the series andethylene polymers are recovered,wherein,additional co-catalyst is injected in at least a subsequent reactor ofthe series.

Advantageously no catalyst is injected in the last reactor, preferablycatalyst is injected only in the first reactor.

In a preferred embodiment there are only two reactors in the series. Inanother preferred embodiment at least one of the reactors in the seriesis a loop reactor. In another embodiment all the reactors are loopreactors. In another embodiment the polymerization in all reactors ofthe series is performed under slurry conditions and advantageously theethylene polymers consist of solid particles and are in suspension in adiluent. In another embodiment the slurry contents of the reactors arecirculated continuously with a pump to maintain efficient suspension ofthe polymer solid particles in the liquid diluent. In another embodimentthe reactors are liquid full loop reactors. The process of the inventioncan comprise any combination of at least two of the above embodiments.

In a most preferred embodiment the process of the present invention iscarried out in two loop reactors under slurry conditions.

Advantage of the process of the present invention is mainly to decreasecatalyst consumption for the same polyethylene production, in otherwords to increase the productivity (Productivity is in g of polyethyleneper g of catalyst).

The present invention also relates to the following improvement:

In a process for the preparation of ethylene polymers using a number ofreactors arranged in series comprising the steps in whicha) ethylene, a diluent, a catalyst, a co-catalyst and optionallycomonomers and hydrogen are introduced into a first reactor,b) polymerization of ethylene and optionally comonomers is carried outin the reaction mixture of said first reactor to make ethylene polymers,c) reaction mixture is discharged from said first reactor,d) said reaction mixture and fresh ethylene and optionally comonomersand hydrogen are introduced into the consecutive reactor to makeadditional ethylene polymers,e) said reaction mixture is discharged from said consecutive reactor andintroduced into the further consecutive reactor, if any, with freshethylene and optionally comonomers and hydrogen to make additionalethylene polymers, steps c) and d) are repeated until the last reactorof the series,f) reaction mixture is discharged from last reactor of the series andethylene polymers are recovered,the improvement wherein,additional co-catalyst is injected in at least a subsequent reactor ofthe series, amount of catalyst injected is reduced and the productioncapacity of the reactors in series is unchanged.

Preferred embodiments are the same as above.

Advantageously no catalyst is injected in the last reactor, preferablycatalyst is injected only in the first reactor.

DETAILED DESCRIPTION OF THE INVENTION

Olefin co-monomers which are suitable for being used in accordance withthe present invention may comprise but are not limited to aliphaticC₃-C₂₀ alpha-olefins. Examples of suitable aliphatic C₃-C₂₀alpha-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene and 1-eicosene.

Diluents which are suitable for being used in accordance with thepresent invention may comprise but are not limited to hydrocarbondiluents such as aliphatic, cycloaliphatic and aromatic hydrocarbonsolvents, or halogenated versions of such solvents. The preferredsolvents are C₁₂ or lower, straight chain or branched chain, saturatedhydrocarbons, C₅ to C₉ saturated alicyclic or aromatic hydrocarbons orC₂ to C₆ halogenated hydrocarbons. Nonlimiting illustrative examples ofsolvents are butane, isobutane, pentane, hexane, heptane, cyclopentane,cyclohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane,isooctane, benzene, toluene, xylene, chloroform, chlorobenzenes,tetrachloroethylene, dichloroethane and trichloroethane.

According to the present invention the term “catalyst” is defined hereinas a substance that causes a change in the rate of a polymerizationreaction without itself being consumed in the reaction. According to apreferred embodiment said catalyst is a metallocene or chromiumcatalyst. According to another embodiment, said catalyst may also be aZiegler-Natta catalyst. In another particularly preferred embodiment,said catalyst may comprise any catalyst which is provided on a Sisupport.

The metallocene catalysts are compounds of Group IV transition metals ofthe Periodic Table such as titanium, zirconium, hafnium, etc., and havea coordinated structure with a metal compound and ligands composed ofone or two groups of cyclopentadienyl, indenyl, fluorenyl or theirderivatives. Use of metallocene catalysts in the polymerization ofolefins has various advantages. Metallocene catalysts have highactivities and are capable of preparing polymers with enhanced physicalproperties in comparison with the polymers prepared using Ziegler-Nattacatalysts. The key to metallocenes is the structure of the complex. Thestructure and geometry of the metallocene can be varied to adapt to thespecific need of the producer depending on the desired polymer.Metallocenes comprise a single metal site, which allows for more controlof branching and molecular weight distribution of the polymer. Monomersare inserted between the metal and the growing chain of polymer.

The term “metallocene catalyst” is used herein to describe anytransition metal complexes consisting of metal atoms bonded to one ormore ligands. In a preferred embodiment, the metallocene catalyst has ageneral formula MX, wherein M is a transition metal compound selectedfrom group IV and wherein X is a ligand composed of one or two groups ofcyclopentadienyl (Cp), indenyl, fluorenyl or their derivatives.Illustrative examples of metallocene catalysts comprise but are notlimited to Cp₂ZrCl₂, Cp₂TiCl₂ or Cp₂HfCl₂.

The metallocene catalysts generally are provided on a solid support. Thesupport should be an inert solid, which is chemically unreactive withany of the components of the conventional metallocene catalyst. Thesupport is preferably a silica compound.

The term “chromium catalysts” refers to catalysts obtained by depositionof chromium oxyde on a support, e.g. a silica or aluminum support.Illustrative examples of chromium catalysts comprise but are not limitedto CrSiO₂ or CrAl₂O₃.

The term “Ziegler-Natta catalyst” refers to a catalyst of the generalformula MX_(n) wherein M is a transition metal compound selected fromgroup IV to VII, wherein X is a halogen, and wherein n is the valence ofthe metal. Preferably, M is a group IV, group V or group VI metal, morepreferably titanium, chromium or vanadium and most preferably titanium.Preferably, R is chlorine or bromine, and most preferably, chlorine.Illustrative examples of the transition metal compounds comprise but arenot limited to TiCl₃, TiCl₄. In a particularly preferred embodiment ofthe invention said catalyst is a titanium tetrachloride (TiCl₄)catalyst.

Ziegler-Natta catalysts generally are provided on a support, i.e.deposited on a solid support. The support should be an inert solid,which is chemically unreactive with any of the components of theconventional Ziegler-Natta catalyst. The support is preferably a silicaor magnesium compound. Examples of the magnesium compounds which are tobe used to provide a support source for the catalyst component aremagnesium halides, dialkoxymagnesiums, alkoxymagnesium halides,magnesium oxyhalides, dialkylmagnesiums, magnesium oxide, magnesiumhydroxide, and carboxylates of magnesium.

The term “co-catalyst” as used herein is defined as a catalyst that canbe used in conjunction with another catalyst in order to improve theactivity and the availability of the other catalyst in a polymerisationreaction. Such co-catalysts may include organometallic compounds, or amixture of non-coordinated Lewis acids and alkylaluminiums as it is wellknown in the art.

Preferably, organometallic compounds of periodic groups I to III areused as co-catalyst according to the present invention. In aparticularly preferred embodiment, said co-catalyst is a catalystsuitable for being used in conjunction with a metallocene catalyst andis an organoaluminium compound, being optionally halogenated, havinggeneral formula AlR₃ or AlR₂Y, wherein R is an alkyl having 1-16 carbonatoms and R may be the same or different and wherein Y is hydrogen or ahalogen. Examples of co-catalysts comprise but are not limited totrimethyl aluminum, triethyl aluminum, di-isobutyl aluminum hydride,tri-isobutyl aluminium, tri-hexyl aluminum, diethyl aluminum chloride,or diethyl aluminum ethoxide. A particularly preferred co-catalyst foruse in the present invention is tri-isobutyl aluminium.

The polymerization reaction can be carried out at a temperature of from50 to 120° C., preferably at temperature of from 70 to 115° C., morepreferably at temperature of from 80 to 110° C., and at a pressure offrom 20 to 100 bars, preferably at pressure of from 30 to 50 bars, morepreferably at pressure of 37 to 45 bars.

Injection of co-catalyst in at least one of the subsequent reactor ofthe series is made under usual conditions in such polymerizations. Theman skilled in the art knows how to inject co-catalyst in a reactor. Hebegins to inject co-catalyst in at least one of the subsequent reactorof the series until he notices a reduction of the off gas of saidsubsequent reactor. By way of example:

-   -   X is the concentration of co-catalyst injected in the first        reactor, X is based on the fresh diluent injected in the first        reactor,    -   the concentration of co-catalyst to be injected in at least one        of the subsequent reactors and based on the fresh diluent        injected in said subsequent reactor is between 0.1 X and X and        advantageously between 0.3 X to 0.6 X.

As used herein, the term “polymerization slurry” or “polymer slurry”means substantially a multi-phase composition including at least polymersolid particles and a liquid phase, the liquid phase being thecontinuous phase. The solids include catalyst and polymerized olefin,such as polyethylene. The liquids include an inert diluent, such asisobutane, with dissolved monomer such as ethylene and optionally one ormore co-monomer, molecular weight control agents, such as hydrogen,antistatic agents, antifouling agents, scavengers, and other processadditives.

Suitable inert diluents (as opposed to solvents or monomers) are wellknown in the art and include hydrocarbons which are inert or at leastessentially inert and liquid under reaction conditions. Suitablehydrocarbons include isobutane, n-butane, propane, n-pentane,isopentane, neopentane, isohexane and n-hexane, with isobutane beingpreferred.

By way of example, such polymerization double loop reactor working witha Ziegler-Natta catalyst, consisting of two interconnected loopreactors, whereby the reaction conditions are different in each of saidloop reactors may be used to produce high molecular weight ethyleneco-polymers in a first reactor and a low molecular weight ethyleneco-polymers in a second reactor. Reactants fed to the first reactor maycomprise ethylene, hexene, isobutane diluent, and hydrogen.Concentration of reactants in the first reactor may then for instancecomprise 1% w/v ethylene, 3% w/v hexene, and a low concentration ofhydrogen. The reaction temperature may comprise around 83 to 88° C. andpolyethylene co-polymers having a density comprised around 0.925 g/cm³may be obtained. Polymer slurry may be transferred to the secondreactor, wherein further ethylene is fed, preferably to obtain aconcentration of 4% w/v in the reactor and hydrogen is added, preferablyto obtain a concentration of 2 vol % in the reactor. Preferably, noadditional catalyst is added in the second reactor. Also, preferably nohexene co-monomer is added in the second reactor and co-monomerconcentrations in the second reactor result from the transfer ofco-monomer together with polymer slurry from the first reactor.Generally residence time of the slurry in the reactor is higher in thefirst reactor than in the second reactor.

Examples

In the following examples catalyst is injected only in the firstreactor.

Example 1: Comparative example, no injection of Tibal in second reactor.

Example 2: Injection of Tibal in second reactor.

The catalyst is a Ziegler-Natta.

Tibal (tri isobutyl aluminum) in first reactor is injected in thecatalyst feed line of the first reactor. Pre-contact between catalystand co-catalyst is short.

Tibal in second reactor is injected directly in the second reactor.Tibal concentration added in second reactor is based on fresh isobutaneinjected in second reactor.

The activity and productivity are computed as follows:

Activity in Reactor 1 [g/g/h/% C₂ ⁻]=productivity in Reactor 1[g/g]/(residence time[h]*C₂ ⁻OG [%]). C₂ ⁻OG means concentration ofethylene in Off gas.Residence time [h]=(reactor volume [m³]*d_(slurry) [kg/m³]*solids)/PEthroughput [kg/h] Same for reactor 2. Productivity is in g ofpolyethylene per g of catalyst.

Examples 1 2 1st reactor Tibal (ppm) 511 462 C2− (kg/h) 21 22 C6− (cc/h)1.6 1.6 H2 (Nl/h) 2.2 2.2 res. time (min) 61.2 60.6 C2− (wt %) in offgas 0.58 0.59 2nd reactor Tibal (ppm) 0 345 C2− (kg/h) 24 25 H2 (Nl/h)1050 900 res. time (min) 32.4 32.4 C2− (wt %) in off gas 3.19 2.94 H2(vol %) in off gas 2.17 1.63 Final product MI5 (g/10′) 0.53 0.47 HLMI(g/10′) 15.4 13.4 density (g/cc) 0.9478 0.9471 Productivity & activityProductivity (g/g) 9080 9796 Activity Rx1 (g/g/h/% C2) 7641 8104Activity Rx2 (g/g/h/% C2) 2623 3134

1-10. (canceled)
 11. A process for the preparation of ethylene polymerscomprising: introducing ethylene, a diluent, a catalyst, a co-catalystand optionally comonomers and hydrogen into a first loop reactor to forma first reaction mixture, polymerizing ethylene and optionallycomonomers in the first reaction mixture to form ethylene polymers,discharging the first reaction mixture from the first loop reactor,introducing the first reaction mixture and fresh ethylene and optionallycomonomers and hydrogen into one or more second reactors to formadditional ethylene polymers within a second reaction mixture, whereinthe polymerization in all reactors is performed under slurry conditions,and wherein the one or more second reactors are arranged in series anddownstream from the first loop reactor and wherein one or more secondreactors comprise loop reactors; discharging the second reaction mixturefrom the one or more second reactors; and recovering ethylene polymer,wherein additional co-catalyst is injected in at least one of the secondreactors such that the concentration of co-catalyst injected in the atleast one of the second reactors, and based on the fresh diluentinjected in the at least one of the second reactors, is between 0.1 Xand X, wherein X is the concentration of co-catalyst injected in thefirst loop reactor based on the fresh diluent injected in the first loopreactor, and the production capacity of each reactor is essentiallyunchanged from a process wherein additional co-catalyst is not injectedin at least one of the second reactors; wherein catalyst is injectedonly into the first loop reactor, and wherein the catalyst is aZiegler-Natta catalyst of a general formula MX_(n), wherein M is atransition metal compound selected from Groups IV to VII of the PeriodicTable, wherein X is a halogen, wherein n is the valence of M, andwherein the Ziegler-Natta catalyst is deposited on a solid silicasupport.
 12. The process of 11, wherein the comonomers are introducedinto the first loop reactor, and comprise aliphatic C₃-C₂₀alpha-olefins.
 13. The process of claim 13, wherein the comonomers arepropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene. 14.The process of claim 13, wherein the comonomer is hexene, and wherein nohexene is added to the one or more second reactors.
 15. The process ofclaim 11, wherein the diluent is an aliphatic hydrocarbon solvent, acycloaliphatic hydrocarbon solvent, an aromatic hydrocarbon solvents.16. The process of claim 16, wherein the diluent is halogenated.
 17. Theprocess of claim 11, wherein the diluent is a C₁₂ or lower saturatedhydrocarbon, a C₅ to C₉ saturated alicyclic or aromatic hydrocarbons, ora C₂ to C₆ halogenated hydrocarbon.
 18. The process of claim 11, whereinthe diluent is butane, isobutane, pentane, hexane, heptane,cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylene, chloroform,chlorobenzene, tetrachloroethylene, dichloroethane, or trichloroethane.19. The process of claim 11, wherein the co-catalyst is a mixture of anon-coordinated Lewis acid and an alkylaluminum.
 20. The process ofclaim 11, wherein the co-catalyst is an organometallic compound.
 21. Theprocess of claim 20, wherein the organometallic compound has a generalformula AlR₃, wherein R is an alkyl having 1-16 carbon atoms and each Rmay be the same or different.
 22. The process of claim 20, wherein theorganometallic compound has a general formula AlR₂Y, wherein R is analkyl having 1-16 carbon atoms and each R may be the same or different,and wherein Y is hydrogen or a halogen.
 23. The process of claim 11,wherein the co-catalyst is trimethyl aluminum, triethyl aluminum,di-isobutyl aluminum hydride, tri-isobutyl aluminum, tri-hexyl aluminum,diethyl aluminum chloride, or diethyl aluminum ethoxide.
 24. The processof claim 11, wherein polymerization is carried out at a temperature offrom 50° C. to 120° C., and at a pressure of from 20 bars to 100 bars.